Uncertainty in health risks due to anthropogenic primary fine particulate matter from different source types in Finland

The emission-exposure and exposure-response (toxicity) relationships are different for different emission source categories of anthropogenic primary fine particulate matter (PM_2.5). These variations have a potentially crucial importance in the integrated assessment, when determining cost-effective abatement strategies. We studied the importance of these variations by conducting a sensitivity analysis for an integrated assessment model. The model was developed to estimate the adverse health effects to the Finnish population attributable to primary PM_2.5 emissions from the whole of Europe. The primary PM_2.5 emissions in the whole of Europe and in more detail in Finland were evaluated using the inventory of the European Monitoring and Evaluation Programme (EMEP) and the Finnish Regional Emission Scenario model (FRES), respectively. The emission-exposure relationships for different primary PM_2.5 emission source categories in Finland have been previously evaluated and these values incorporated as intake fractions into the integrated assessment model. The primary PM_2.5 exposure-response functions and toxicity differences for the pollution originating from different source categories were estimated in an expert elicitation study performed by six European experts on air pollution health effects. The primary PM_2.5 emissions from Finnish and other European sources were estimated for the population of Finland in 2000 to be responsible for 209 (mean, 95% confidence interval 6–739) and 357 (mean, 95% CI 8–1482) premature deaths, respectively. The inclusion of emission-exposure and toxicity variation into the model increased the predicted relative importance of traffic related primary PM_2.5 emissions and correspondingly, decreased the predicted relative importance of other emission source categories. We conclude that the variations of emission-exposure relationship and toxicity between various source categories had significant impacts for the assessment on premature deaths caused by primary PM_2.5.     

The seasonal cycles and photochemistry of C2–C5 alkanes at Mace Head

Continuous in-situ measurements of NMHCs at Mace Head, Ireland during two full annual cycles from January 2005 to January 2007 were used to investigate NMHC emission sources and transport including dilution and photochemical oxidation. The Mace Head research station is ideally located to sample a wide range of air masses including polluted European transport, clean North Atlantic and Arctic air masses and the ultra-clean, Southern Atlantic air masses. The variety in air mass sampling is used to investigate interaction of emissions, transport, dilution and photochemistry. Variability of long-lived hydrocarbon ratios is used to assess and estimate typical transport times from emission source to the Mace Head receptor. Seasonality in the ratios of isomeric alkane pairs (for butane and pentanes) are used to assess the effects of atmospheric transport and photochemical ageing. Finally, the natural logarithms of NMHC ratios are used to assess photochemical oxidation.     

Influence of boundary conditions on CMAQ simulations over the Iberian Peninsula

The influence of chemical boundary conditions (BC) on the response of the Community Multiscale Air Quality (CMAQ) model over the Iberian Peninsula was investigated in this study. Three strategies to supply boundary conditions in the context of the Integrated Assessment Modelling System for the Iberian Peninsula (SIMCA) were tested. Alternative methods consist in providing BC from (1) fixed, time-independent, concentration profiles, (2) concentrations predicted in a CMAQ mother domain (48 km, 1 h resolution) and (3) concentration values from the GEOS-Chem chemical-transport global model (2 × 2.5°, 3 h resolution). High resolution (3 km) simulated concentrations of the main pollutants (NO₂, NO, SO₂, O₃, PM₁₀ and PM_2.5) were compared through a comprehensive statistical analysis including observational data from 165 monitoring stations all over the Iberian Peninsula. It was found that model sensitivity to BC for nitrogen and sulphur oxides was limited, being restricted to the vicinity of model boundaries. However, significant domain-wide differences were found when modelling ozone and PM depending on the BC provided to run the tests. Although model performance was affected by spatial and seasonal factors, the results indicate that model-derived, dynamic BC improved CMAQ predictions when compared to those based on static concentrations prescribed in the boundaries. Aggregated statistics suggest that the GEOS-Chem produced the best results for O₃ and PM_2.5 while NO₂ and PM₁₀ were slightly better predicted under the CMAQ nesting approach. Besides the statistical evaluation some other relevant issues in the context of Integrated Assessment Modelling (IAM) are discussed to gain a better insight into the suitability of the methods analyzed and limitations of downscaling methods. Despite being useful to get a better understanding of the role of BC in SIMCA, this study contributed to highlight model deficiencies and therefore to point out future research needs to improve IAM activities in the Iberian Peninsula.     

Assessment of the uncertainty of using an inverse-dispersion technique to measure methane emissions from animals in a barn and in a small pen

Dispersion techniques are useful for assessing the effectiveness of management practices in mitigating methane (CH₄) emissions from animal operations. In this paper, the accuracy of an inverse-dispersion technique was examined for two common situations: 1) emissions from animals in a barn and 2) emissions from animals in a pen. For both situations, the accuracy of emission estimates generally increased with increasing fetch (scaled to barn height, h, or to pen width, X_s) between the source and the concentration measurement. The gas recovery ratio increased from 0.66 at 5 h to 0.93–1.03 at 10 h–25 h for the barn, and decreased from 1.59 at 0 X_s to 0.99 at 5 X_s and from 1.54 at 0 X_s to 1.09 at 5 X_s for the two small pen scenarios, due to the declining sensitivity of the dispersion model to errors in wind complexity and errors in the assumed source configuration. However, the relative uncertainty of the measured concentration increased with fetch due to the decreasing gas concentrations. Hence, improving the accuracy of emission estimates is a compromise between the source configuration sensitivity and the concentration measurement sensitivity. Fetches of about twice the size of the pen and about 10 times the height of the barn are suggested.     

Large-scale mercury variations in Lake Vänern (Sweden) 1974-98

Lake V?nern, the largest lake in Sweden, has been seriously contaminated with mercury during the 20th century. In the 1970's and 80's the direct load, mainly from a chlor-alkali industry in the area, of mercury was drastically reduced as a response to new legislation, from three to five tons down to between five and ten kg yr(-1). Large amounts of the disposed pollutant have accumulated in the sediments. The question posed in this work is now, is the effect of the drastic load reduction after more than two decades visible in the sediments? The question is relevant as large areas still are blacklisted for fishing, but also as a follow-up of a major remedy action. The lake also serves as a freshwater reservoir for even Sweden's second largest city. This work synthesises and compares data of mercury in the sediments from three major field programs, in 1974, 1984 and 1998. The interest is focused on both spatial heterogeneity and temporal trends. In 1974, the surface concentrations are significantly higher than in subsequent surveys. Significant differences are also found between 1984 and 1998. Significant spatial differences within the lake are found for respective year. The most contaminated area is located in the north, close to the major point source (a former chlor-alkali industry). This is also the area with the largest improvement, as a direct response to the reduction in load. Further from the outlet, the recovery is more affected by burial and transport processes out into the deeper basins.     

The collection of PM10 for toxicological investigation: comparisons between different collecting devices

A positive correlation has been established between increased levels of airborne particulate pollution and adverse health effects, the toxicological mechanisms of which are poorly understood. For toxicologists to unambiguously determine thesemechanisms, truly representative samples of ambient PM₁₀ are required. This presents problems, as PM₁₀ collecting equipment commonly employed, such as the Tapered Element Oscillating Microbalance (TEOM®), heat the inflow toexclude moisture or use fibrous filters, resulting in a PM₁₀sample that may have undergone significant chemical change on thefilter surface or is contaminated by filter fibres. Other systems(i.e. Negretti and Partisol) can successfully collect PM₁₀ without chemical alteration or filter contamination. Comparativecollections from Port Talbot, S. Wales suggest that TEOMs and Negretti/Partisol systems collect different PM₁₀'s; the principle difference arising from the TEOM's heating chamber, which precipitates water-soluble ions and volatilises some organic components. This results in both the mass and compositionof the PM₁₀'s being altered. Particle size distributionsfor Negretti and Partisol collections highlighted differences mainly attributed to different flow rates. The results of thiswork demonstrate that simple correlations between PM₁₀ massand adverse health effects are problematic. Furthermore, elucidation of the complex fractionation and chemical changes indifferent collectors is necessary.     

Macroinvertebrate Regionalisation for use in the Management of Aquatic Ecosystems in Victoria, Australia

The development of a broader, more holistic approach to aquaticecosystem management has been called for in recent years. Physical and chemical objectives alone are no longer consideredsufficient for the protection of aquatic ecosystems and shouldbe supplemented with biological objectives. The ubiquitousand sedentary nature of macroinvertebrates, combined with theirmeasurable response to environmental conditions, favour their use as important indicators in environmental policies. To establish biological objectives, there is a need for a regionalframework to limit the variability between ecosystems. Past studies have demonstrated that an a posteriori regionalisationapproach may be more useful than an a priori approach in explaining single component (e.g. macroinvertebrates) patternsacross ecosystems. This is particularly important as aquaticresource management agencies often focus on one or twocomponents of the ecosystem to assess environmental health. This study uses an a posteriori method to delineate and describebiological regions based on edge and riffle macroinvertebrate data. The regionalisation will provide a framework for settingbiological objectives, based on the range of reference conditionsmeasured within each separate region. The objectives will includeregional checklists for taxa and biotic indices. Predictive modelling in the style of RIVPACS or AUSRIVAS will also be usedwithin each region to develop objectives, incorporating local, regional and systematic features as predictor variables.     

Economic and Spatial Impacts of an Existing Reserve Network on Future Augmentation

An optimization model for land reservation was developed that explicitly selects parcels in the most compact or contiguous manner possible while meeting habitat requirements and a budget limitation. The model was used to compare the effects of an existing reserve network on future parcel spatial locations and total cost. Using habitat and land value data from Josephine County, Oregon, it was found that a system of existing reserves created by various policies and overseen by different agencies can decrease future reserve compactness and contiguity, and increase total cost. This work suggests that coordinated planning can result in more efficient conservation efforts for less cost.     

Mechanistic studies of N-nitrosodimethylamine (NDMA) formation in chlorinated drinking water

Studies were conducted to investigate the hypothesis that N-nitrosodimethylamine (NDMA) is a potential disinfection by-product specifically produced during chlorination or chloramination. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed by the reaction of DMA with free chlorine in the presence of ammonia and also with monochloramine. We proposed a mechanism for NDMA formation in chlorinated or chloraminated water, which does not require nitrite as in N-nitrosation. The critical NDMA formation reactions consist of (i) the formation of monochloramine by combination of free chlorine with ammonia, (ii) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (iii) the oxidation of UDMH by monochloramine to NDMA, and (iv) the reversible chlorine transfer reaction between free chlorine/monochloramine and DMA which is parallel with (i) and (ii). A kinetic model was also developed to validate the proposed mechanism.     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.